Process for breaking petroleum emulsions



Patented July 1, 1952 a corporation 011 Delaware No Drawih'g. ApplicationAugnst 14, 1950, Serial No. 179,398

9 Claims. 1;-

This invention relates to petroleum emulsionsof the water-in-oil type that are commonly re-- ferred' to as cut oil, "roily oil, emulsified oil etc., and which comprise droplets of naturally-occurring waters or brines dispersed in amore' orless permanent state throughout the oil which constitutes the continuous phase: ci the emulsion.

One object of my invention isto provide a novelprocessfor breaking or resolving emulsions of the referred to.

Another object of my invention is to provide an economical and rapid process for separating; emulsions which have been prepared under con:- trolled conditions from mineral oil, such crude oil and relatively soft waters; or weak brinesi Controlled emul's-i fication and subsequent demursification under the conditions justmentioned, are of significant value in removing: impurities particularly inorganic salts trom pipeline oil.

Demulsificationas contemplated in: the present application includes the preventive step. of commi-ngling the demulsi fier' with. the aqueous component which would or might subsequently become either phase of the emulsion, absence of such precautionary TEGEESIIIEEL Similarly, suchdemul'sifier' may be mixedwitlr the hydrocarbon component.

The demulsifiying agent employed in: thepresout process: is a; tremotional= ester: obtained from: a polycarboxy' acid and. a. dick obtained by the oxypropylation of 2-ethylhexandiol-l,3-. Thec'ommerciali brand of. this diol v is sold under the name of octylen'eglycolt oro'ctylene diol. Momen tari'ly ignoring certain: variants of. structure which; wilLbe considered; subsequently the den'iulsifier may be exemplified by the following. formula:

11 11 est- 1n. Htjn Ho Eta aha t H- i i 2 noocyn ao ooiuotoo- 1 o ctuuo tlr aa ooomfl" n H H in which n andn are numerals including with the proviso. that nplus 1:. equals a sum varying. from 15 to 80'; n" is a whole number not over 2. and- R is the radicalof the polycarboxy radical coon R/ oooncw and preferably free from any radicals having more than 8 uninterrupted carbon atoms in a single group, and with the further proviso that the parent diol prior to esterification be water insoluble and kerosena-solubfea Attention is directed to the co-pending appIi=- cation of C.-

Blair, Jr Serial No. 70,821 filed J anuary I3, 1949'- (nowPatent Not 2,562,878, dated- August 7, 1951-), in which there is described,- among other things; a-process-for petro leum emulsionsof the water-*in-oil type charac' terized by subjecting the emulsion to the action. of an esterifi cation product oi a dicarboxylic-acifdand apolyalkyle'ne' glycol which the ratio. of. equivalents of polybasie acid to: equivalents of olyalkylene glycol is therange of 01s to 210; inwhich the alk-ylene group has from' 2170 3 car'- bon atoms, and whicli the' molecular weight of the product is between L,5"0o"and 4,000:

similarly, there have been used? esters of; di' carboxy acids and polypropylene gl'ycols which: 2 moles of the dicarboxy acid ester have; been reacted with one: mole of a polypropylene glycol having a molecular weight, for example, or 2,000? so as to form an acidic fractional. ester... Examinati-on of what is said subsequently herein as well as the thereto appended claimsin comparison with the previous example will show the line or delineation between such somewhat.- compa rable' compounds Of greater significance, how-- ever, is what is said subsequently in regard; to thestructure of the parent diol as compared: to polypropylene glycols' whose molecular weights may vary from 1,000 to 2,000.

For convenience, what is said hereinafter will be divided into five parts:

Part 1 is concerned with the preparation of. the oxypropyla-tion derivatives ofv theo'ctylene glycol;

Part 2'is concerned with the preparationof the esters from the oxypropylated derivative;

Part 3-is concerned with a consideration of thestructure of the" diols which is of significance in, light of What issaid subsequently,

Part 4 is concerned with the use of the prod-- ucts herein described as demuls-i-fiers for breaking. water-in-oil emulsions; and q Part 5 is concerned with certain derivatives; which can be obtained from the oxypropylated diols. In some instances, such derivativesare obtained by modestoxyethylation. preceding the oxypropylation step, or o-xyp-ropylat'ion followed by oxye'thylation. This results. in diols having. somewhat. difierent' properties which can then be reactediwi'th the same poI ycarboXy acids or anhydrides described .Part 2 .to give effective d'emul'sifying agents. For this reason a description of the apparatus makes casual mention of oxyethyla'tion, For theLsa'me reason there is brief" mention of the use of gl'ycide'.

PART 1- For a number of Well lmownreasons equip-- ment, whether laboratory size, semi-pilot plant size, pilot plant size, or large scalei'size; is'no't' as a 3 rule designed for a particular alkylene oxide. Invariably and inevitably, however, or particularlyin the case of laboratory equipment and pilot plant size the design is such as to use any of the customarily available alkylene oxide, i. e., ethylene oxide, propylene oxide, butylene oxide, glycide, epichlorohydrin, styrene oxide, etc. In

the subsequent description of the equipment it becomes obvious that it is adapted for oxyethylation as well as oxypropylation.

Oxypropylations are conducted under a wide variety of conditions, not only in regard to presence or absence of catalyst, and the kind of oata-- lyst, but also in regard to the time of reaction temperature of reaction, speed of reaction, pres sure during reaction, etc. For instance, oxyalkylations can be, conducted at temperatures up to approximately 200 C. with pressures in about the same range up to about 20 pounds per square inch. They can be conducted also at temperatures approximating the boiling point of water or slightly above, as for example 95 to 120 C. Under such circumstances the pressure will be less than 30 pounds per square inch unless some special procedure is employed as is sometimes the case, to wit, keeping an atmosphere of inert gas such as nitrogen in the vessel during the reaction. Such low temperature-low reaction' rate oxypropylations have been described very completely in U. S. Patent No. 2,448,664. to H. R. Fife et, al., dated September 7, 1948. Low temperature, low pressure oxypropylations are particularly desirable Where the compound being subjected to oxypropylation contains one, two or three points of reaction only, such as monohydric alcohols, glycols and triols.

Since low pressure-low temperature reaction speed oxypropylations require considerable time, for instance, 1 to 7 days of 24 hours each to complete the reaction they are conducted as a rule whether on a laboratory scale, pilot plant scale, or large scale, so as to operate automatically. The prior figure of seven days applies especially to large-scale operations. I have used conventional equipment with two added automatic features; (a) a solenoid controlled valve which shuts off the propylene oxide in event that the temperature gets outside a predetermined and set range, for instance, 95 to 120 C., and (b) another solenoid valve which shuts off the propylene oxide (or for that matter ethylene oxide if it is being used) if the pressure gets beyond a predetermined range, such as 25 to 35 pounds. Otherwise, the equipment is substantially the same as is commonly employed for this purpose where the pressure of reaction is higher, speed of reaction is higher, and time of reaction is much shorter. In such instances such automatic controls are not necessarily used.

Thus, in preparing the various examples I have found it particularly advantageous to use laboratory equipment or pilot plant which is designed to permit continuous oxyalkylation whether it be oxypropylation or oxyethylation. With certain obvious changes the equipment can be used also to permit oxyalkylation involving the use of glycide where no pressure is involved except the vapor pressure of a solvent, if any, which may have been used as a diluent.

As previously pointed out the method of using propylene oxide is the same as ethylene oxide. This point is emphasized only for the reason that the apparatus is so designed and constructed as to use either oxide.

The oxypropylation procedure employed in the 4 preparation of the oxyalkylated derivatives has been uniformly-"the same particularly= in light of the fact that a continuousautomatically-controlled procedure was employed. In this procedure the autoclave was a conventional autoclave made of stainless steel and having a capacity of approximately 15 gallons and a working pressure of one thousand pounds gauge pressure. This pressure obviously is far beyond any requirement asiarias propylene oxide goes unless there is a reaction of explosive violence involved due to ,accident.. The autoclave was equipped 3 With'the conventional devices and openings, such as the variable-speed stirrer operating at speeds from R. P. M. to 500 R. P. M.; thermometer well and thermocouple for mechanical thermometer; emptying outlet; pressure gauge, manual vent line; charge hole for initial-reactants; at least one connection forintroducing the alkylene oxide, such aspropylene oxide or ethylene oxide, to the bottom of the autoclave; along with suitable devices fonboth cooling and heating the autoclave, such as a cooling jacket, and, preferably, coils in addition thereto, with the jacket so arranged that it is suitable for heating with steam or cooling with water and further equipped with electrical heating devices. Such autoclaves are, of course, in essence small-scale replicas of the usual conventional autoclave used in oxyalkylation procedures. In some instances in exploratorypreparations an autoclave having a smaller capacity, for instance, approximately 3 /2 liters in one case and about 1% gallons in another case, was used.

Continuous operation, or substantially continuous operation, was achieved by the use of a separate container to hold the alkylene oxide being employed, particularly propylene oxide. In conjunction with thesmaller autoclaves, the container consists essentially of a laboratory bomb having a capacity of about one-half gallon, or somewhat in excess thereof. In some instances a larger bomb was used, to wit, one having a capacity of about one gallon. This bomb was equipped, also, with an inlet for charging, and an eductor tube going to the bottom of the container so as to permit discharging of alkylene oxide in the liquid phase to the autoclave. A bomb having a capacity or about pounds was used in connection with the l5-gallon autoclave. Other conventional equipment consists, of course, of the rupture disc, pressure, gauge, 'sightfeed glass, thermometer connection for nitrogen for pressuring bomb, etc. The bomb was placed on a scale during use. The connections between the bomb and the autoclave were flexible stainless steel hose or tubing so that continuous weighings could be made without breaking or making any connections. This applies also to the nitrogen line, which was used to pressure the bomb reservoir. To the extent that it was required, any other usual conventional procedure or addition which provided greater safetywas used, of course, such assafety glass protective screens, etc. V

Attention is directed again to what has been I said previously in regard to automatic controls which shut off the propylene oxide in event temperature of reaction passes out of the predetermined range or if pressure in the autoclave passes out of predetermined range. With this particular arrangement practicall all oxypropylations become uniform in that the reaction temperature was held within a few degrees of any selected point, for instance, if

C. was selected as the operating temperature the maximum point would be at the most 110 C. or

scale or dial scale holding the propylene oxide bomb was so set that when the predetermined amount of propylene oxide had passed into the reaction the scale movement through a time operating device was set for either one to two hours so that reaction continued for 1 to 3 hours after the final addition of the last propylene oxide and action was comparatively slow undersuch conditions as compared with oxyalkylations at 200? C. Numerous reactions were conducted in which the time varied'from one day (24 hours) up to three days "(72 hours), for completion of the final member of a series. In some instances the reaction may take place in considerablyless time, i; e., 24 hoursor less, as far as a partial oxypropylation is concerned. .The minimum time recorded was about a 3-hour period in a single step. Reactions indicated as being complete in 9 hours may have been complete in a lesser period of time in light of the automatic equipment employed. In the addition of propylene oxide, in they autoclave equipment as far as possible the valves were set so all the propylene oxide if fed continuously would be added at a rate so that. the predetermined amount would react within the first 15.hours of the 24-hour period or two-thirds of any shorter period. This meant thatifthe reaction was interrupted automatically for a period of time for pressure to drop or. temperature to drop the predetermined amount-of oxide would still be added in most instances well within the predetermined time period. Sometimes where the addition was a comparatively small amount in a 12-hour period there would be an unquestionable speeding up of the reaction, by simply repeating the example and using 6, 8 or 9 hours instead of 12 hours.

When operating at-a comparatively high temperature, for instance, between 150 to 200 C., an unreacted alkylene oxide such as propylene oxide, makes its presence felt in the increase in pressure or the consistency of a high pressure. However, at a low enough temperature it may happen that the propylene oxide goes in as a liquid. If so, andif it remains unreacted there is, of course, an inherent danger and appropriate steps must be taken to safeguard against this possibility; if need be a sample must be withdrawn and examined for unreacted propylene oxide. One obviousprocedure, of course,.is to oxypropylate-at a modestly higher temperature, for instance, at 140 to 150 C. Unreacted oxide afiectsdetermination of the acetyl or hydroxyl value-of the hydroxylated compound obtained.

The higher the molecular weight of the compound, i. e., towards the latter stages of reaction, the longer the time required to add a given amount of oxide. One possible explanation is that the molecule, being larger, the opportunity for random reaction is decreased. Inversely, the lower the molecular weight the faster the reaction takes place. For this reason, sometimes at least, increasing the concentration of the catalyst does not appreciably speed up the reaction, particularly when the product subjected to oxyalkylation hasa comparatively high molecular weight. However, as has been pointed out previously, 'operatingat a low pressure and a low temperature even in large scaleoperations as much as a week or ten days time may lapse to obtain some of thehigher molecular weight derivatives from monohydric or' dihydric ma- 3.1 I 1 In a number-of operations the counterbalance thereafter the operation was shut down. This particular device is particularly suitable for use '10.

on larger equipment than laboratory size autoclaves, to wit, on semi-pilot plant or pilot plant size, as well as on large scalesize.

stirring period is intended to avoid th presence This final of unreacted oxide.

- In this, sort of operation, of course, the temperature range was controlled automatically by either use of cooling water, steam, or electrical heat, so as to raise or lower the temperature. The pressuring of the propylene oxide into the reaction vessel was also automatic insofar that the feed stream was set for a sloW continuou run which was shut off in casethe pressure passed a predeterminedpoint as previously set out. All thepoints of design, ,construction, etc., were conventional including the gases, check valves and entire equipment. As far as I am aware at least I Example 10.

The particular autoclave employed was one with a capacity of approximately 15 gallons, or on the average of about 120 pounds of reaction mass. The speed of the stirrer could be varied from 150 to 340 R. P. M. Y 8% pounds of octylene glycol were charged into the autoclave along with I ceeding.

one'pound of sodium hydroxide. The reaction pot was flushed out with nitrogen. The autoclave was sealed, the automatic devices adjusted, and set for injecting a total of 50 /3 pounds of propylene oxide in a 9-hour period. The pressure regulator was set for a maximum of approximately 35 pounds per square inch. This meant that the bulk of the reaction could take place, and probably did take place, at a lower pressure. This comparatively low pressure was the-result of the fact that considerable catalyst was present, propylene oxide was added comparatively slowly and, more important, the selected temperature range was 205" to 21551 (about the boiling point of water) The initial introduction of propylene oxide was not started until the heating devices had raised the temperature to approximately the boiling point of water. At the completion of the reaction a sample was taken and oxypropylation proceeded as in Example 2a, immediately suc- Ewmmple 2a Slightly over 52 pounds of the reaction mass identified as Example To, were permitted to remain in the reaction vessel and without the addition of any more catalyst approximately 43 pounds more of propylene oxide were added.

The oxypropylation was conducted in substan- ,ter, xylene and kerosene.

"TA B LEl g t Composition Before Composition at End A V b 'H d Max 1 T 4 V Y Y res. ime H. C. Oxide Cata- Theo. H. C.* Oxide Cata- Deter S P lbs. Hrs.

' Amt. Amt. lyst M01. Amt. Amt. lyst min. sq. in.

LbS. Lbs Lbs. Wt. I bS. LbS. Lbs.

' The hydroxylatod compound is octyleneglycol.

the end of the reaction periodpart of the sample was withdrawn and oxypropylation was continued as described in Example 3a, following.

Exampl eta.

Approximately 61 pounds of the reaction mass identified as Example 2a, preceding, was permitted to stay in the reaction vessel. 35 /3 pounds of propylene oxide were introduced during this third period. No additional catalyst was added. The conditions of reaction; as far as temperature and pressurefwere concerned were substantially the same as in'Example 1a, preceding. The re-' action time was cut down to 4 ,4; hours. At the completion of the reaction part of the reaction mass was withdrawn and the remainder subjected to oxypropylation as described in Example 4d, succeeding.

Example 4a '70 pounds of the reaction mass were permitted to remain in the autoclave. No additional catalyst was introduced. Slightly over 19 pounds of propylene oxide Were introduced in the same manner as described in Example la, preceding. Conditions in regard to temperature and pressure were substantially th same. In this instance the oxide was introduced in 2% hours. At the end of the reaction period part of the sample was withdrawn and the remainder of the reaction mass subjected to further oxypropylation as described in Example c, succeeding.

Example 5a Approximately 78 pounds of reaction mass were permitted to stay in the autoclave. This was subjected to reaction with slightly over 12 pounds of propylene oxide. Conditions of reaction were substantially the same as described in Example 111 as far "as temperature and pressure were concerned;v ,The period required'for addition of this oxide was Thours."

Whathasf been said herein is presented in tabular form in Table 1 immediately following, with some added information as to molecular weight and as to solubility of the reaction product in Wa- Example 1a was dispersible to insoluble in water but completely soluble in xylene and kerosene; Examples 20. through 6a, inclusive were all insoluble in water but completely soluble in xylene and kerosene.

The final product, i. e., at the end of the oxypropylation step, was a somewhat viscous very pale straw-colored fluid which was Wa-ter-insoluble. This is characteristic of all various end products obtained in this series. These products were, of course, slightly alkaline due to the residual caustic soda employed. This would also be the case if sodium methylate were used as a catalyst.

Speaking of insolubility in water or solubility in kerosene'such solubility test can be made simply by shaking small amounts of the materials in a test tube withwater, forinstance, using 1% to'5% approximately based on the amount of water present.

Needles to say, there is no complete conversion of propylene oxide into the desired bydroxylated compounds. This is indicated by the fact that the theoretical molecular weight based on a statistical average is greater than the molecularweight .calculated by usual methods on basis of acetyl or hydroxyl value. Actually, there is no completely satisfactory method for determining .moleculaiiweights of these types of compounds with a highdegree of accuracy when the molecular weights exceed 2,000. In some instancesthe acetyl value or hydroxyl value serves as satisfactorilyas an index to the molecular weight as any other procedure, subject to the above limitations, and especially in the higher molecular weight range. If any difficulty is encountered in the manufacture of the esters as described'in Part 2 the stoichiometrical amount of acid or acid compound should be taken which corresponds to the indicated acetyl or hydroxyl value. This matter has been discussed in the literature and is a matter of common knowledge .and requires no further elaboration. In fact, it is illustrated by some of the examples appearing in the patent previously mentioned.

60 PART 2 As previously pointed out the present invention is concerned with acidic esters obtained from the oxypropylated derivatives described in Part 1, immediately preceding, and polycarboxy acids, particularly dicarboxy acids such as adipic acid, phthalic acid, or anhydride, succinic acid, diglycollic acid, sebacic acid, azelaic acid, aconitic acid, maleic acid or anhydride, citraconic acid or anhydride, maleic acid or anhydride adducts as obtained by the Diels-Alder reaction from reactants such as maleic anhydride and cyclopentadiene. Such acids should be heat stable so they are not decomposed during esterification. They may contain as many as 36- carbon atoms as, for

glycols or other hydroxylated compounds i well I known. Needless to say, various compounds may be used such as the low molal ester, the anhydride, the acyl chloride, etc. However, for purpose of economy it is customary to use either the acid or the anhydride. A conventional procedure is employed. On a laboratory scale one can employ a resin pot of the kind described in U. S. Patent No. 2,499,370, dated March 7, 1950, to De Groote and Keiser, and particularly with one more Opening tto permit the use .of a porous spreader if hydrochloric acid gas is to be used as a catalyst. Such device or absorption spreader consists of minute Alundum thimbles which are connected to a glass tube. One can add a sulfonic acid such as para-toluene sulfonic acid as a catalyst. There is-some objection to this because in some instances there is some evidence that this acid catalyst tends to decompose or rearrange oxypropylated compounds, and particularly likely to do sozif the esterification temperature is too high. In the case of polycarboxy acids such as .diglycollic acid, which is strongly acidic there is 'noneed to add any catalyst. The

use of hydrochloric gas has one advantage over paratoluene sulfonic. acid and that is that at the end of the reaction it can be removed by flushing out with nitrogen, whereas there is no reasonably convenient means available of removing the paratoluene sulfonic acid or other sulfonic acid employed. If hydrochloric acid is employed one need only pass the gas through at an exceedingly slow rate so asto keep the reaction mass acidic. Only a trace of acid need be present. I have em: ployed hydrochloric acid gas or the aqueous acid itself to eliminate the initial basic material. My preference, however, is to use no catalyst whatsoever and to insure complete dryness of the diol as described in the final procedure just preceding of Table 2. w

The products obtained in Part 1 preceding may contain a basic catalyst. As a general procedure I have added an amount of half-concentrated hydrochloric acid considerably in excess of what is required to neutralize the residual catalyst. The mixture is shaken thoroughly and allowed to stand overnight. It is then filtered and refluxed with the xylene present until the water can be separated in a phase-separating trap. As soon as the product is substantially free from water the distillation stops. This preliminary step can be carried out in the flask to be used for esterification. If there is any further deposition of sodium chloride during the reflux stage needless to say a second filtration may be required. In any event the neutral or slightly acidic solution of the oxypropylated derivatives described in Part 1 is then diluted further with suflicient xylene decalin, petroleum solvent, or the like, so that one has obtained approximately a 65% solution. To this solution there is added a polycarboxylated reactant. as previously described. such as phthalic anhydride, succinic acid or anhydride, ."diglycollic acid, etc. The

10 mixture is refluxed until esterification is complete as indicated byelimination'of water or drop in carboxyl value. Needless'to say, if one produces a half-ester from an anhydride such as phthalic anhydride, no water is eliminated. However, if it is obtained from diglycollic acid, for example, water is eliminated. All such procedures are conventional and have been so thoroughly described in the literature that further consideration will be limited to a few examples and a comprehensive table.

Other procedures for eliminating the basic residual catalyst, if any, can be employed. For

v example, the oxyalkylation can be conducted acid present as a catalyst.

45 ml., 237 C.

in absence of a solvent or the solvent removed after oxypropylation. Such oxypropylation end product can then be acidified with just enough concentrated hydrochloric acid to just neutralize the residual basic catalyst. To this product one can then add a small amount of anhydrous sodium sulfate (sufiicient in quantity to take up any water that is present) and then subject the mass to centrifugal force so as to eliminate the hydrated sodium sulfate and probably the sodium chloride formed. The clear somewhat viscous straw-colored amber liquid so obtained may contain a small amount of sodium sulfate or sodium chloride but, in any event, is perfectly acceptable for esterification in the manner described.

It is to be pointed out that the products here described are not polyesters in the sense that there is a plurality. of both diol radicals and acid radicals; the product is characterized by having only one diol radical.

In some instances and, in fact, in many instances I have found that in spite of the dehydration methods employed above that a mere trace of water still comes through and that this mere trace of water certainly interferes with the acetyl or hydroxyl value determination, at least when a number of conventional procedures are used and may retard esterification, particularly where there is no sulfonic acid or hydrochloric Therefore, I have preferred 'to use the following procedure: I have employed about 200 grams of the diol as described in Part 1, preceding; I have added about 60 grams of benzene, and then refluxed this mixture in the glass resin pot using a phase-separating trap until the benzene carried out all the water present as water of solution or the equivalent. Ordinarily this refluxing temperature is apt to be in the neighborhood of 130 to possibly 150 C. When all this water or moisture 'h as been removed I also withdraw approximately 20 grams or a little less benzene and then add the required "amount of the carboxy reactant and also about 150 grams of a high boiling aromatic petroleum solvent. These solvents are sold by various oil refineries and. as far as solvent effect act" asif they werealmost completely aromatic in character. Typical distillation data in the particular type I have employed and found very satisfactory is the following: Y

I. B. P... 142 C. 50 ml., 242 C. 5 m1., 200 C. 55 1111., 244 C. 10 ml., 209 C. 60 1111., 248 C. 15 m1., 215 C. 65 1111., 252 C.- 20 m1., 216 C. '70 1111., 252 C. 25 m1., 220 C. ml.,.260' .C.i 30 ml., 225 C.' ml., 264 'C. 35 ml., 230? C. 8.5 m'l.,270 1C;

40 1111.,234 C. ml., 2809C.

, .11 ,..12. After this material is added, refluxing is contintures, such as decalin and xylene, can be emued and, of course, is at a high temperature, to ployed. V wit, about 160 to 170 C. If the carboxy re- The data included in the subsequent tables, 1. 6.,

actant is an anhydride needless to say no water Tables 2 and 3, are self-explanatory, and very of reaction appears; if the carboxy reactant is 5 complete and it is believed no further elaboration an acid water of reaction should appear and is necessary:

' TABLE 2 E N f Ex. N0. Theo HTAIBO. 1 Actual 401. 911. 1 1g. 1 31,

x. 0.0 of Hyy roxy ase on o y Acid Ester droxy of V. of ggg Actual Cmp'd. Poly Garbo Reactant gzggggg Ompd. H.C H.V. (grs.) (gm) 16 999 112 134 105 260 D1 1 661116 801d 76.0 10, 999 112 134 105 200 M91616 Anhyd- 55.6 16 999 112 134 105 200 1 116161164611 34.0 16 999 112 134 105 200 ACOnitlC Acid. 93.1 16 999 112 134 105 200 1161 116 4616... 33.0 20 1, 830 61. 2 79. 3 1, 416 200 Diglycollic acid 18. 8 26 1, 330 61. 2 19. 3 1, 416 200 P11013116 .41111y 23. 5 2a. 1, 830 61. 2 79. 3 1, 416 200 Maleic Anhyd- 16.3 26 1,3 61.2 19.3 1,416 200 AODllitic .4616... 15.3 26 1,330 61.2 19.3 1,416 200 Adipic .46 20.6 26 1, 330 61. 2 93. 5 1, 136 200 D1g1 661116 80ld 41. 26 1,330 61.2 93.5 1,136 200 M31616 Anhy 345 3a 2, 826 39.0 77. 1 l, 474 200 Diglycollic Acld... 36. 4 36 2,326 39.0 11.1 1,414 200 P11c116116A1111 d. 40.2 36 2,326 39.0 11.1 1,414 200 M61616 Anhyd 26.6 36 2,326 39.0 11.1 1,414 200 AGOllitiC Acid 41.4 36 2,326 39.0 11.1 1,414 200 461 116146111 39.3 46 3,125 30. 0 62. 1,194 200 D1 1 661116 Acid. 14. 9 46 3,125 30.0 62.5 1,194 200 P11012116 411111 11. 13.4 46 3,125 30. o 62. 5 1, 194 200 M61616 Anhyd. 12. 9 46 3,125 30.0 62.5 1,194 200 1466111116 14616 11.3 46 3,125 30.0 62.5 1,194 200 4111 16 Acid 16.2 46 3,125 30.0 19.0 1,413 200 D1 1 661116 .4616 31.3 52 4,826 23.2 52.4 2,140 200 do 12.5 56 4,326 23.2 52.4 ,140 200 Phthal'c Anhyd 15.5 56 4,326 23.2 52.4 2,140 200 M31616 141111 111 10.3 56 4,326 23.2 52.4 2,140 200 AOODlfiO Acid 10.3 56 4,326 23.2 52.4 2,140 200 Adi 16 Acid..." 13.6 511 4,826 23. 2 64. 6 1, 734 200 Dig ycolhc Acid 30. 8 56 4,326 23.2 64.6 1,134 200 M31616 Anhyd 22.5 56 4,326 23.2 64.6 1, 4 200 1461136 4616... 33:6 611 5, 565 20. 1 46.3 2, 420 200 Diglycolhc A01 11. 1 66 5,565 20,1 46.3 2, 200 P10116116 Anhyd 13.1 66 5,565 20.1 46.3 2,420 200 M91616 Anhyd 9.6 66 5,565 20.1 46.3 2,420 200 1166111116 .461 9.6 66 5,565 20.1 46.3 2, 420 200 401616 A0 12.0 66 5,565 20.1 60.2 1,360 200 D1 1 661116461 1 23.6 62 5, 565 20. 1 60. 2 1, 860 200 Maleic Anhyd 21. 0

should be eliminated at the above reaction tem- 7 TABLE 3 perature. If it is not eliminated I simply separate out another or cc. of benzene by Esterlfiva- Time of Water id 3 1 1 'r E 111 means of the phase-separatmg trap and thus iagi r Solvent @12 5 o? 653111;?) raise the temperature to or C., or even 45 to 200 C., if need be. My preference is not to 266 4% 8,5 go above 200 C. 1 256 139 4 None 234 2 2 1 0. The use of such solvent is extremely sat1sfac- 299 8 14 8 tory provided one does not attempt to remove 274 192 5% 919 213 132 2 4.0 the solvent subsequently except by vacuum dis- 213 161 4 4.0 tillation and provided there is no objection to a little residue. Actually, when these materials 216 196 5 2 U are used for a purpose such as demulsification the solvent 248 203 3% 5 Solvent #7-3... 312 127 3% solvent mlght ust as well be allowed to remain. 232 192 5,1 If the solvent is to be removed by distillation, 10y and particularly vacuum distillation, then the 264 178 2% 14 high boiling aromatic petroleum solvent might 9%;; well be replaced by'some more expensive solvent, 213 191 4 14 such as decalin or an alkylated decalin which f has a rather definite or close range boiling point. 212 1,, 316 The removal of the solvent, of course, is purely a conventional procedure and requires no elab- 212 131 11 2 I1 oration 43 13 1 In the appended table Solvent #'73, which 210 194 1244 35 appears in numerous instances, is a mixture of 7 volumes of the aromatic petroleum solvent pre- 229 235 3 2.5 viously described and 3 volumes of benzene. This 3g was used, or a similar mixture, in the manner 206 193 314 2.6 previously described. A large number of the ex- 5V2 amples indicated employing decalin were redo 223 133 11 5.5 peated, using this mixture and particularly with P 171 84 p the preliminary step of removing all the water. If one does not intend to remove the solvent my The procedure for manufacturing the esters preferenceistouse the petroleum solvent-benzene has been illustrated by preceding examples. mixture although obviously any of the other mix- 7 If for any reason reaction does not take place in a manner that is acceptable, attention should be directed to the following details: (a) Recheck the hydroxyl or acetyl value of the oxypropylated diol and use a stoichiometrically equivalent amount of acid; (b) if the reaction does not proceed with reasonable speed either raise the temperatures indicated or else extend the period of time up to 12 or 16 hours if need be; (c) if necessary, use /2% of paratoluene sulfonic acid or some other acid as a catalyst; (d) if the esterification does not produce a clear product a check should be made to see if an inorganic salt such as sodium chloride or sodium sulfate is not precipitating out. Such salt should be eliminated, at least for exploration experimentation, and can be removed by filtering. Everything else being equal as the size of the molecule increases and the reactive hydroxyl radical represents; a smaller fraction of the entire molecule and thus more difliculty is involved in obtaining complete esterification.

Even under the most carefully controlled conditions of oxypropylation involving comparatively low temperatures and long time of reactio there are formed certain compounds lwhose composition is still obscure. "Such side reaction products can contribute a substantial proportion of the final cogeneric reaction mixture. Various su gestions have been made as to the nature of these compounds, such as being cyclic polymers of propylene oxide, dehydration products with the appearance of a vinyl radical, or isomers of propylene oxide or derivatives thereof, i. e., of an aldehyde, ketone, or allyl alcohol. In some instances an attempt to react the stoichiometric amount of a polycarboxy acid with the oxypropylated derivative results in an excess of the carboxylated reactant for the reason that apparently under conditions of reaction less reactive hydroxyl radicals are present then indicated by the hydroxyl value. Under such circumstances there is simply a residue of the carboxylic reactant which can be removed by filtration or, if desired, the esterification procedure can be repeated using an appropriately reduced ratio of carboxylic reactant. I

Even the determination of the hydroxyl value and conventional procedure leaves much to be desired due either to the cogeneric materials previously referred to, or for that matter, the presence of any inorganic salts or propylene oxide. Obviously this oxide should be eliminated.

The solvent employed, if any, can be removed from the finished ester by distillation and particularly vacuum distillation. The final products or liquids are generally pale amber to amber in color, and show moderate viscosity. They can be bleached with bleaching clays, filtering chars, and the like. However, for the purpose of demulsification or the like color is not a factor and decolorization is not justified.

In the above instances I have permitted the solvents to remain present in the final reaction mass; In other instances I have followed the same procedure using decalin or a mixture of decalin and benzene in the same manner and ulti mately removed all the solvents by vacuum distillation. Appearances of the final products are much the same asthe diols before esterification and in some instances were somewhat darker in color and had a reddish cast and perhaps somewhat more viscous.

PART 3 Previous reference has been made to the fact that diols such as polypropylenegiycol of approximately 2,000 molecular weight, for example, have been esterified with dicarboxy acids and employed as demulsifying agents. On first examination the difierence between thelierein described productsand such comparable products appears to be rather insignificant; In fact, the difference is such that it fails'toexpla'in the fact that compounds of the kind herein described may be, and frequently are, 10%, 15% or 20% better on a quantitative basis than thesimpler compound previously described, and demulsify faster and give cleaner oil in many instances; The method of making such comparative tests has been described in a booklet entitled ".Treating Oil Field Emulsions, used in the Vocational training courses, Petroleum Industryseries, of the American Petroleum Institute.

The difference, of course, does not reside in the carboxy acid but in the diol. Momentarily an efiort will be made to emphasize'certain things in regard to the structure of a polypropylene glycol,.such as polypropylene glycol of a 2000 molecular weight. Propylene glycol has a primary alcohol radical and a secondary alcohol radical. In this sense the building unit which forms polypropylene glyools is not symmetrical. Obviously, then, polypropylene glycols can be obtained, at least theoretically, in which two secondary alcohol groups are united or a secondary alcohol group is united to a primary alcohol group, ether- .ization being involved, of course, in each instance.

Usually no effort is ;I nade to difierentiate between oxypropylation taking place, for example, at the primary alcohol unit radical or the secondary alcohol radical. "Actually, "when such products are obtained, such as a high molal polypropylene glycol or the products obtained in the manner herein describ'ed one does not obtain a single derivative such as 11-10(RO) H in which n has one and only one value, forinstance, 14,15 or 16, or the like. Rather, one obtains a cogeneric mixture of closely related or touching homologues. These materials invariably have high molecular weights and cannot be separated from one another by any known procedure without decomposition. The properties of such mixture represent the contribution of the various indi v vidual members of the mixture. On a statistical basis, of course, 11. can be appropriately specified. For practical purposes one need only consider the oxypropylation'of a monohydric alcohol because Y in essence this is substantially the mechanism involved. Even in such instances where one is concerned with a monohydric reactant one cannot draw a single formula and say that by following such procedure one can readily obtain or or of such compound. However, in the case of. at least monohydric initial reactants one can readily draw the formulas of a large number of compounds which appear in some of the probable mixtures or can be prepared as components and mixtures which are manufactured conventionally.

Simply by "way of illustration reference is made to the copending application of De Groote, Wirtel, and Pettingill, Serial No. 109,791, filed August 11, 1949 (now Patent No. 2,549,434, dated April 17, 1951).

However, momentarily referring again to a monohydric initial reactant it is obvious that if one selects any such simple hydroxylated compound and subjects such compound to oxyalkylation, such as oxyethylation, or oxypropylation, it becomes obvious that. one is really producing a '15 polymer of the alkylene oxides except for the terminal group. This'is particularly true where the amount of oxide added'is comparatively large, for instance, 10, 20, 30, 40, or 50 units. If such compound is subjected to oxyethylation soas to introduce units of ethylene oxide, it is well known that onedoes not obtain a single constituent which, for the sake of convenience, may be indicated as RO(C2H4O)30H. Instead, one obtains a cogeneric mixtureof' closely related homologues, in which the formula may be shown as the following, ROKCzI-RO) nI-I, wherein n, as far as the statistical averagegoes, is 30, but the individual members present in significant amount may vary from instances where n has a value of 25, and perhaps less, to a point where n may represent or more. Such mixture is, as stated, a cogeneric closely related series of touching homologous compounds. Considerable investigation has been made in regard to the distribution curves for linear polymers. Attention is directed to the article entitled Fundamental Principles of Condensation Polymerization, by Flory, which appeared in Chemical Reviews, volume 39, No. 1, page 137,

Unfortunately, as has been pointed out by Flory and other investigators, there is no satisfactory method, based on either experimental or methematical examination, of indicating the exact proportion of the various members of touching homologous series which appear in cogeneric condensation products of the kind described. This means that from the practical standpoint, i. e.,-the ability t'o'describe how to make the product under consideration and how to repeat such production time after time without difficulty, it is necessary to resort to some other method of description, or else consider the value of n, in formulas such as those which have appeared previously and which appear in the claims, as representing both individual constituents in which ,n has a single definite value, and also with the understanding that n represents the average statistical value based on the assumption of completeness of reaction.

This may be illustrated as follows: Assume that in any particular example the molal ratio of the propylene oxide to the diol is 15 to 1. Actually, one obtains products in which n probably varies from 10 to 20, perhaps even further. The average value, however, is 15, assuming, as previously stated, that the reaction is complete. The product described by the formula is best described also in terms of method of manufacture. H

However,- in the instant situation it becomes obvious that if an ordinary high molal propyleneglycol is compared to strings of white beads of various lengths, the diols herein employed as intermediates are characterized by the presence of a black head, .i. e., a radical which cor responds to octyleneglycol or octylenediol as previously described, i. e., the radical ence non HCIIH nHHH r v H H H I 7 Furthermore, it becomes obvious that one now has a nonsymmetrical radical in the majority of cases for the reason that in the cogeneric mixture going back to the original formula n 11(311 m sn H611 HCHHH nand-n are usually not equal. For instance, if one introduces 15 moles of propylene-oxide, n and 11/ could not be equal, insofar that the nearest approach to equality is where the value of n is 7 and n is 8. However, evenin the case ofan even number such as 20, 3'0, 40 or 50, it is also obvious that n and n will not be equal in light of what has been said previously. Both sides of the molecule are not going to grow with equal rapidity, i. e., to the same size. Thus the diol herein employed is differentiated from polypropylene diol 2000, for example, in that (a) it carries a hetero unit, i. e., a unitother than a propylene glycol or propylene oxide unit, (b) such unit is oficenter, and (c) the effect'of that unit, of course, must have some effect in the range with which the linear molecules can be drawn together by hydrogen binding or van der Waals forces, or whatever'else may be involved. V V

What has been said previously. can be emphasized in the following .manner. It has, been pointed out previously that in the last formula immediately preceding-11 or ,n could be zero. Under the conditions, of manufacture as described 7 in Part lit is extremely unlikely that n ever zero. However, such compounds can be prepared readily with comparatively little difficulty by resorting to a blocking effect or reaction. Forinagainst the presence of any water, it becomes evident that all the propylene oxide introduced, for instance 15 to molecules per polyhydric alcohol molecule necessarily must enter at one side only, If such product is then saponified so as to decompose the acetic acid ester and then acidified so as to liberate the water-soluble acetic acid and the water-insoluble diol a separation can be made and such diol then subjected to esterification as described in Part 2, preceding. Such esters, of course, actually represent products where either it or n is zero. Also intermediate procedures can be employed, i. e., following the same esterification step after partial oxypropylation. For instance, one might cxypropylate with one-half the ultimate amount of propylene oxide to be used and then stop the reaction. One could thenconvert thispartialoxypropylated intermediate into an ester by reaction of. one mole'of acetic acid with one mole of a diol. This ester could then be oxypropylated with all the remaining propylene oxide. The final product so obtained could be saponified and acidified so as to eliminate the watersoluble acetic acid and free the obviously unsymmetrical diol which, incidentally, should also be kerosene-soluble.

From a practical standpoint I have found no advantage in going to this extra step but it does emphasize the difference in structure between the herein described diols employed as intermediates and high molal polypropylene glycol, such as polypropylene glycol 2000. V v

attest- :Conventional-.rlemulsifying agents employed in the treatment :of': oil ifield emulsions :are used as such, or after dilution with any .:suitable solvent,

such as water, .pet'roleum hydrocarbons, such as benzene, itoluene,.ixylene,-tar acid oil, cresol, an- 'thraceneoilgetci Alcohols;Iparticularlyiailphatic alcohols, such i as imethyl -a;lcohol, ethyl alcohol,

denatured alcohol, propyl alcohol, 'butyl al'cohol, hexyl alcohol, octyI a1c0h0l, etc., may be 'employed as diluents. Miscellaneous solvents suchas pine oil, carbon tertachloridejsulfur dioxide extract obtained in therefining'of petroleum, etc., may be employed as diluents. :Similarly, the material or materials employed aslthe demulsifying agent of 'my process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

. It is well known that conventional demulsifying agents may be used in'a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, oreven 1 to-40,000,

or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not si nificant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials employed as the demulsifying agent of my process. 0

'In practicing my process for resolving petroleum emulsions of the water-in-oil type, a treating agent or demulsifying agent of the kind above described is brought into contact -with'or caused to act upon the emulsion tobe treated, in-any of the various apparatus now generally used to resolve or break petroleum emulsions'with a chemical-reagent, the above procedure being used-alone or in combination with'o ther demulsiiyingprocedure, such as the electrical dehydration process.

One type of procedure is to accumulate a volume of emulsified oil in a tank and conduct a batch treatment type of demulsification procedure to recover clean'oil. In this procedure the emulsion is admixed with the demulsifier, for example by agitating the tank of emulsion and slowly dripping demulsifier into the emulsion. In some cases mixing is achieved by heating "the emulsion while dripping in the demulsifier, depending upon theconvection currents in the emulsion to produce satisfactory admixture. 'In

a third modification of this type of treatment,"a circulatingw pump withdraws emulsion from; e.-'g.,

the bottom of the tank, and reintroduces it into the top of the tank, the demulsifier being added, for example, at the suction side of said circulating pump.

In a second type of treating procedure, the demulsifier. is introduced into the wellfiuids at the well-head or at some'ipoint betweenithe'wellhead and the final oil storage 'tank,';by'means of an adj ustable" proportioning mechanism vor 'proportioning pump. Ordinarily theiiow, of :fluids through the subsequent lines and fittings sufilces .to p'roduce ithe "desireddegrjee' of mixing of de- "mulsifier and emulsion, although in some {iiicedure," the ,systemniay include various'nnechanical devices for"withdrawlng'free water, sepa- "rati-ng entrained water, or accomplishing ,quies- 'c'lent settling orthe' chemicaliz'ed emulsion. 'lI-Ieating devices may Jliketvisebe incorporated in any of thetreating procedures described. herein.

"A third type of application (down-the-hole) of demulsifierto emulsion isto introduce the demulsifier eitherperiodically. or continuously in diluted 'or undiluted ,formiinto'ithe "w'e11 .and'to allow it tocome'tothe .s'urfa'celwiththe well fluids, and then to flow the chemicalized emulsion through any .desirable surface'equipment, such as employe'd'inlthe .other'treating .procedures. This particular a-typeof application .is

decidedly vuseful when theidemul'sifier' is .used in sion separates and settles-from the mass.

The following is a typical installation. A reservoir to hold-Zthedemulsifier of the kind described (diluted or undiluted) is placed at the well-head I where xthe iefliuentxliquids leave .the

well. This -reservoir:1or ;container, which 'may vary from 5 gallons-to igallonsiforconvenience, is: connected toia proportioning pump which :in-

jects the demulsifieri'drop-wise into'ithe. fluids leaving :theiwell. -Suchchemicalized fluids :pass through the flowline into -ai settl-ingftank. The settling tank consists of a tanks-of any convenient'. size, for instance, one Which will hold amounts: of ifluidtproduced in 4 -to24 =hours (500 barrels to 2000 :barrels capacity), and in which there is a perpendicular conduit 1 from the top permit the incomingiifiuids to pass-from the top of the settlingv tank-to thebottom, so that such of thetank to almost' the very rbottomso as to incoming fluids do not disturb Stratification "which takes place-'during -the course of demulsification. The =settlingtank has two outlets, one

being below the water level to drain ofi thewater resulting from demuls'ification oraccompanying i the emulsion as free water, the other being an stances additional mixing devices mayjbein'trooil outletatthe top to permit the passage-of dehydrated oil to -a-second tank,--being a storage --tank, which holds pipeline or dehydrated oil.

If desired, the conduitorpipe which serves to carry the fluids from the'well to the settling tank may include -a -secti'onof pipe wi-th bafiies to serve as a mixer,-to insurethorough distribution {of-the demulsifier throughout the -fluids,- or -a heater for raising the temperature-of thefluids to some convenient temperature, 'for instance,

3120" to F., or both "heater-and mixer. 65

Demulsification procedure isistartedby simply setting the pump so "as' tofeed acomparatively -large ratio of demulsifier," for instance, 1:5;000.

As soonas'a complete"break or'satisfactory' demulsification is obtained,thepumpfiis regulated until experience shows that theiamount of demulsifier being added is. just ,sufiicient' to. producelclean or dehydratedfoil. "The amount being fed at suclfstageiisusually 1': 10,000, 1 15,000,

1':20,000.orthe'1ike: V

In many instances the oxyalkylatd products herein specified as demulsifiers can be,- conveniently used without dilution} However, as previ- "vary, depending uponthe solubility characteristics of the oxyalkylated product, and of course Will be dictated in part by economic considerations, i. e., cost.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed withsome other chemical demulsifier. A mixturejwhich illustrates such combination is the following:

Oxyalkylated derivative, for example, the product of Example 321), 20%;

A cyclohexylamine salt of a polypropylated naphthalene mono-sulfonic acid, 24%;

'An ammonium salt'oi a polypropylated naphthalene mono-sulfonic acid, 24%

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol,

The above proportions are all weight percents.

PART 5 Previous reference has been made to other oxyalkylating agents other than propylene oxide, such as ethyleneoxide. Obviously variants can be prepared which, do not depart from what is said herein but do produce modifications. The diol 2-ethy1hexandiol-1,3 can be reacted with ethylene oxide in modest amounts and then subjected to oxypropylation provided that theresultant derivative is (a) water-insoluble, (b) kerosene-soluble, and (c) has present 15 to 80 alkylene oxide radicals. Needless to say, in order to have water-insolubility and kerosene-solubility the large majority must be propylene oxide. Other variants suggest themselves as, for example, replacing propylene oxide by butylene oxide.

More specifically then one mole of 2-ethylhexandiol-1,3 can be treated with 2,4 or 6 moles of ethylene oxide and then treated with propylene oxide so as to produce a water-insoluble, kerosene-soluble diol in which there are present 15 to 80 oxide radicals as previously specified. Similarly the propylene oxide can be added first and then the ethylene oxide, or random oxyalkylation can be employed using a mixture of the two oxides. The compounds so obtained are readily esterified in the same manner as described in Part 2, preceding. Incidentally, the diols described in Part 1 or the modifications described therein can be treated with various reactants such as glycide, epichlorohydrin, dimethyl sulfate, sulfuric acid, maleic anhydride, ethylene imine, etc. If treated with epichlorohydrin or mono-chloroacetic acid the resultant product can be .further reacted with a tertiary amine such as pyridine,'or the like, to give quaternary ammonium compounds. If treated with maleic anhydride to give a total ester the resultant can be treated with sodium bisulfite to yield a sulfosuccinate. Sulfo groups can be introduced also by means of a sulfating agent as previously suggested, or by treating the chloroacetic acid resultant with sodium sulflte.

I have found that if such hydroxylated compound or compounds are reacted further so as to produce entirely new derivatives, such new derivatives have the properties of the original hydroxylated compound insofar that they are effective and valuable demulsifying agents for resolution of water-in-oil emulsions as foundin the petroleum industry, as break inducers in doctor treatment of sour crude, etc.

Having thus described my invention,, what I claim as new and desire ,to secure by Letters Patent, is: ,7 g g 1'. A process for, breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including hydrophile synthetic products; said hydrophile synthetic products being characterized by the following formula:

in which n and-n are numerals including 0 with the proviso that 11. plus n equals a sum varying from 15 to 80, and n" is a whole number not over 2, and R is a radical of the polycarboxy acid coon in which n" has its previous significance; and

HHHOHv in which 11. and n are numerals including 0 with the proviso that 11 plus n equals a sum varying from 15 to 80, and n" is a whole number not over 2, and R is a radical of the polycarboxy acid COOH in which n" has its previous significance; said polycarboxy acid having not more than 8 carbon atoms; and withthe further proviso that the parent diol prior to esterification be waterinsoluble and kerosene-soluble. r v V 3. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of aj demulsifier including hydrophile synthetic products; said hydrophile synthetic products being characterized by the following formula HcH Hon h in which n" has its previous significance; said polycarboxy acid having not more than 8 carbon atoms; and with the further proviso that the parent diol prior to esterification be water-insoluble and kerosene-soluble.

4. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including hydrophile synthetic products; said hydrophile synthetic products being characterized by the following formula:

Hon

H HOH 22 in which n and n are numerals excluding zero, with the proviso that n plus n equals a sum varying from 15 to 80, and R is the radical of the dicarboxy acid COOH said dicarboxy acid having not more than 8 carbon atoms; and with the further proviso that the parent diol prior to esterfication be water-insoluble and kerosene-soluble.

5. The process of claim 4 wherein the dicarboxy acid is phthalic acid.

6. The process of claim 4 wherein the dicarboxy acid is maleic acid.

7. The process of claim 4 wherein the dicarboxy acid is succinic acid.

8. The process of claim 4 wherein the dicarboxy acid is citraconic acid.

9. The process of claim 4 wherein the dicarboxy acid is diglycollic acid.

MELVIN DE GROO-TE.

REFERENCES GITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,507,560 De Groote et al. May 16, 1950 2,514,399 Kirkpatrick et al. July 11, 1950 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARCTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING HYDROPHILE SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING CHARACTERIZED BY THE FOLLOWING FORMULA: 